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1. Enhanced photodegradation of dimethoxybenzene isomers in/on ice compared to in aqueous solution

   https://doi.org/10.5194/acp-22-5943-2022  

   Hullar, Ted; Tran, Theo; Chen, Zekun; Bononi, Fernanda; Palmer, Oliver; Donadio, Davide; Anastasio, Cort (January 2022, Atmospheric Chemistry and Physics)

   Abstract. Photochemical reactions of contaminants in snow and ice can be importantsinks for organic and inorganic compounds deposited onto snow from theatmosphere and sources for photoproducts released from snowpacks into theatmosphere. Snow contaminants can be found in the bulk ice matrix, ininternal liquid-like regions (LLRs), or in quasi-liquid layers (QLLs) at theair–ice interface, where they can readily exchange with the firn air. Somestudies have reported that direct photochemical reactions occur faster inLLRs and QLLs than in aqueous solution, while others have found similarrates. Here, we measure the photodegradation rate constants for loss of thethree dimethoxybenzene isomers under varying experimental conditions,including in aqueous solution, in LLRs, and at the air–ice interface ofnature-identical snow. Relative to aqueous solution, we find modestphotodegradation enhancements (3- and 6-fold) in LLRs for two of theisomers and larger enhancements (15- to 30-fold) at the air–ice interfacefor all three isomers. We use computational modeling to assess the impact oflight absorbance changes on photodegradation rate enhancements at theinterface. We find small (2–5 nm) bathochromic (red) absorbance shifts atthe interface relative to in solution, which increases light absorption, butthis factor only accounts for less than 50 % of the measured rate constantenhancements. The major factor responsible for photodegradation rateenhancements at the air–ice interface appears to be more efficientphotodecay: estimated dimethoxybenzene quantum yields are 6- to 24-foldlarger at the interface compared to in aqueous solution and account for themajority (51 %–96 %) of the observed enhancements. Using a hypotheticalmodel compound with an assumed Gaussian-shaped absorbance peak, we find thata shift in the peak to higher or lower wavelengths can have a minor tosubstantial impact on photodecay rate constants, depending on the originallocation of the peak and the magnitude of the shift. Changes in other peakproperties at the air–ice interface, such as peak width and height (i.e.,molar absorption coefficient), can also impact rates of light absorption anddirect photodecay. Our results suggest our current understanding ofphotodegradation processes underestimates the rate at which some compoundsare broken down, as well as the release of photoproducts into theatmosphere. 

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2. A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow

   https://doi.org/10.5194/acp-14-1587-2014  

   Bartels-Rausch, T.; Jacobi, H.-W.; Kahan, T. F.; Thomas, J. L.; Thomson, E. S.; Abbatt, J. P.; Ammann, M.; Blackford, J. R.; Bluhm, H.; Boxe, C.; et al (January 2014, Atmospheric Chemistry and Physics)

   Abstract. Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed. 

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3. Sea ice heat and mass balance measurements from four autonomous buoys during the MOSAiC drift campaign

   https://doi.org/10.1525/elementa.2023.00017  

   Perovich, Don; Raphael, Ian; Moore, Ryleigh; Clemens-Sewall, David; Lei, Ruibo; Sledd, Anne; Polashenski, Chris (November 2023, Elem Sci Anth)

   Deming, J.; Nicolaus, M. (Ed.)

   As part of the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC), four autonomous seasonal ice mass balance buoys were deployed in first- and second-year ice. These buoys measured position, barometric pressure, snow depth, ice thickness, ice growth, surface melt, bottom melt, and vertical profiles of temperature from the air, through the snow and ice, and into the upper ocean. Observed air temperatures were similar at all four sites; however, snow–ice interface temperatures varied by as much as 10°C, primarily due to differences in snow depth. Observed winter ice growth rates (November to May) were <1 cm day−1, with summer melt rates (June to July) as large as 5 cm day−1. Air temperatures changed as much as 2°C hour−1 but were dampened to <0.3°C hour−1 at the snow–ice interface. Initial October ice thicknesses ranged from 0.3 m in first-year ice to 1.2 m in second-year ice. By February, this range was only 1.20–1.46 m, due in part to differences in the onset of basal freezing. In second-year ice, this delay was due to large brine-filled voids in the ice; propagating the cold front through this ice required freezing the brine. Mass balance results were similar to those measured by autonomous buoys deployed at the North Pole from 2000 to 2013. Winter average estimates of the ocean heat flux ranged from 0 to 3 W m−2, with a large increase in June 2020 as the floe moved into warmer water. Estimates of average snow thermal conductivity measured at two buoys during periods of linear temperature profiles were 0.41 and 0.42 W m−1 °C−1, higher than previously published estimates. Results from these ice mass balance buoys can contribute to efforts to close the MOSAiC heat budget. 

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4. Wind redistribution of snow impacts the Ka- and Ku-band radar signatures of Arctic sea ice

   https://doi.org/10.5194/tc-17-2211-2023  

   Nandan, Vishnu; Willatt, Rosemary; Mallett, Robbie; Stroeve, Julienne; Geldsetzer, Torsten; Scharien, Randall; Tonboe, Rasmus; Yackel, John; Landy, Jack; Clemens-Sewall, David; et al (January 2023, The Cryosphere)

   Abstract. Wind-driven redistribution of snow on sea ice alters itstopography and microstructure, yet the impact of these processes on radarsignatures is poorly understood. Here, we examine the effects of snowredistribution over Arctic sea ice on radar waveforms and backscattersignatures obtained from a surface-based, fully polarimetric Ka- and Ku-bandradar at incidence angles between 0∘ (nadir) and 50∘.Two wind events in November 2019 during the Multidisciplinary drifting Observatory forthe Study of Arctic Climate (MOSAiC) expedition are evaluated. During both events, changes in Ka- andKu-band radar waveforms and backscatter coefficients at nadir are observed,coincident with surface topography changes measured by a terrestrial laserscanner. At both frequencies, redistribution caused snow densification atthe surface and the uppermost layers, increasing the scattering at theair–snow interface at nadir and its prevalence as the dominant radar scattering surface. The waveform data also detected the presence of previousair–snow interfaces, buried beneath newly deposited snow. The additionalscattering from previous air–snow interfaces could therefore affect therange retrieved from Ka- and Ku-band satellite altimeters. With increasingincidence angles, the relative scattering contribution of the air–snowinterface decreases, and the snow–sea ice interface scattering increases.Relative to pre-wind event conditions, azimuthally averaged backscatter atnadir during the wind events increases by up to 8 dB (Ka-band) and 5 dB (Ku-band). Results show substantial backscatter variability within the scanarea at all incidence angles and polarizations, in response to increasingwind speed and changes in wind direction. Our results show that snowredistribution and wind compaction need to be accounted for to interpretairborne and satellite radar measurements of snow-covered sea ice. 

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5. Development of a snow-firn-ice surface mass balance treatment for ice sheet models

   Pollard, D; DeConto, R. (April 2018, Geophysical research abstracts)

   The treatment of surface melt, runoff, and the snow-firn-ice transition in ice-sheet models (ISMs) is becoming increasingly important, as mobile liquid on Greenland and Antarctic flanks increases due to climate warming in the next century and beyond. Simple Positive Degree Day (PDD)-based box models used in some ISMs crudely capture liquid storage and refreezing, but need to be extended to include vertical structure through the whole firn-ice column, as in some regional climate models (RCMs). This is a necessary prelude to modeling the flow of mobile meltwater in channel-river-moulin systems, and routing to the base and/or margins of the ice sheet. More detailed column models of snow and firn exist, that include compaction, grain size, and other processes. Some focus on dry-snow zones, and have fine vertical resolution spanning the entire firn column with Lagrangian tracking of annual snow layers (e.g., FirnMICE: Lundin et al., J. Glac., 2017). However, they are mostly too computationally expensive for ISM applications, and are not designed for ablation zones with meltwater and bare ice in summer. More general models are used in some RCMs that include similar physics but with fewer layers, and are applicable both to accumulation and ablation zones. Here we formulate a new snow-firn model, similar to those in RCMs, for use within an ice-sheet model. A limited number of vertical layers is used (∼10), with Lagrangian tracking of layers, grain size evolution, compaction, ice lenses, liquid melting, storage, percolation and runoff. Surface melting is computed from linearized net atmospheric energy fluxes, not from PDDs. The model is tested using the FirnMICE experiments, and using gridded RACMO2 modern climate input over Greenland, seeking to balance model performance with computational efficiency. 

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